Method for bonding polyamides to rubber, adhesive for the same, and adhesive coated polyamide reinforcing elements

ABSTRACT

An aqueous alkaline dispersion of a rubbery vinyl pyridine copolymer, trimethylol phenol, and a resorcinol compound, in certain amounts is useful in forming an adhesive for bonding polyamide or nylon cords to rubber compounds or stocks. After dipping the cord in the adhesive dip, the coated cord is heated to dry it and heat cure or heat set the adhesive on the cord. Thereafter, the adhesive containing cord is combined or laminated (calendered) with a curable rubber compound and the resulting assembly is cured. High H-adhesions are obtained with this onestep or single treatment coating dip. It is particularly useful for bonding crystalline polyamides having a large number of aromatic groups in the polymeric structure, e.g., &#39;&#39;&#39;&#39;Fiber B&#39;&#39;&#39;&#39;.

United States Patent 1 Van Gils et a1.

Related US. Application Data Continuation-in-part of Ser. No. 310,524, Nov. 29, 1972, abandoned.

Assignee:

US. Cl. 260/5; 156/110 A; 156/335; 427/385; 260/29.3; 260/838; 260/845; 260/846; 260/839 Int. Cl. C09j 3/12 Field of Search 156/110 A, 335, 110 MD; 161/227, 241, 248, 144, 243, 253, 257; 260/29.3, 838, 846, 345; 117/1388 N, 161

References Cited UNITED STATES PATENTS 10/1947 Compton et al. 161/241 10/1952 Mallory et a1. 260/846 1 June 10, 1975 2,875,179 2/1959 Freeman 260/838 3,023,251 2/1962 Meyers 161/198 3,408,249 10/1968 Brown 161/248 3,437,122 4/1969 Van Gils 161/248 3,517,082 6/1970 Cockerham 156/335 3,547,729 12/1970 Kibler 156/331 3,609,108 9/1971 Kolka et al. 260/838 3,843,484 10/1974 Kamiyoshi et a1. 156/110 A R23,451 l/l952 Mighton 156/110 A Primary ExaminerGeorge F. Lesmes Assistant ExaminerChar1es E. Lipsey [5 7 ABSTRACT An aqueous alkaline dispersion of a rubbery vinyl pyridine copolymer, trimethylol phenol, and a resorcinol compound, in certain amounts is useful in forming an adhesive for bonding polyamide or nylon cords to rubber compounds or stocks. After dipping the cord in the adhesive dip, the coated cord is heated to dry it and heat cure or heat set the adhesive on the cord. Thereafter, the adhesive containing cord is combined or laminated (calendered) with a curable rubber compound and the resulting assembly is cured. High H- adhesions are obtained with this one-step or single treatment coating dip. It is particularly useful for bonding crystalline polyamides having a large number of aromatic groups in the polymeric structure, e.g., Fiber B.

11 Claims, N0 Drawings METHOD FOR BONDING POLYAMIDES TO RUBBER, ADHESIVE FOR THE SAME, AND ADHESIVE COATED POLYAMIDE REINFORCING ELEMENTS This application is a continuation-in-part of prior copending patent application Ser. No. 310,524. filed Nov. 29, 1972, entitled Method for Bonding Polyamides to Rubber, Adhesive for the Same, and Adhesive Coated Polyamide Reinforcing Elements now abandoned.

OBJECTS An object of the invention is to provide a one-step aqueous dip useful in providing an adhesive for bonding polyamide reinforcing elements to rubber compounds, e.g., for binding nylon tire cords to rubber to form carcass and belt plies for making tires. Another object is to provide polyamide reinforcing elements, e.g., such as those used in the belt and the carcass plies of tires, with a minor amount of an adhesive so that the adhesive containing elements may subsequently be bonded to rubber on curing and being characterized by exhibiting high adhesions. A further object is to provide a method for bonding polyamide, particularly aromatic polyamide, fibers, cords and so forth to rubber compounds using a single dip and the product of said method. These and other objects and advantages of the present invention will become more apparent to those skilled in the art from the following detailed description and working examples.

SUMMARY OF THE INVENTION According to the present invention it has been discovered that a composition comprising essentially an aqueous alkaline dispersion generally of 100 parts by weight of a rubbery vinyl pyridine copolymer, from about 2 to 28 parts by weight of trimethylol phenol, from about 0.5 to 24 parts by weight of a water soluble resorcinol compound selected from the group consisting of resorcinol or a resorcinol-formaldehyde non heat hardenable, water soluble and thermoplastic compound (a fusible novolak or novolak resin), from about to 3 parts by weight of an alkaline material selected from the group consisting of NI-I and NaOH, and from about 170 to l 100 parts by weight of water, is very useful as a treating, dipping or coating material for use in bonding polyamide reinforcing elements to rubber compounds. Sufficient alkaline material such as aqueous NI-I or NaOI-I is added to the dispersion (or to one or more of the ingredients of the dispersion before mixing them together) to obtain the desired pH, prevent coagulation of the latex and to provide for stabilization. This will vary with the acidity of the resorcinol or novolak and the pH of the latex, all of which may vary from batch to batch. Since the amount of each compound may vary, the amount of alkaline material required can also vary. After drying the adhesive on the polyamide element to remove water and to heat cure or heat set element can then be combined or calendered with a curable rubber compound and the resulting assembly cured, usually in a mold, to provide a laminate exhibiting high adhesions. This dip is very effective for fibers such as Fiber B. Conventional dips for polyamide or nylon fibers do not give as high adhesions as do the dips ,of the present invention particularly with respect to Fiber B.

Moreover, the present method involves only one dipping step and the process or method can be varied to provide the desired pick-up or solids on the cord by varying the concentration of the dip or speed of cord through the dip to give the amount needed to develop the requisite adhesive bond. Thus, while the cord can be run through successive dips of the same or varying amounts of the above materials to get the desired buildup, this is unnecessary as satisfactory results can be accomplished in one dip. Pre or post dips of other adhesive compositions are unnecessary when using the present aqueous adhesive dip.

DISCUSSION OF DETAILS AND PREFERRED EMBODIMENTS The polyamide, or nylon, reinforcing element of the present invention can be in the form of monofilament, fibers, yarn, tow, twisted yard, cord or fabric. The polyamide may be an aromatic polyamide, an aliphatic polyamide, or a polyamide containing both aliphatic and aromatic units. These long chain polymeric amides are capable of being formed into filaments and have recurring amide groups as an integral part of the main polymer chain. The polyamide ingredient can be a homopolymer, block or random copolymer, or a mixture of two or more of such polymers. The polyamide will usually have both crystalline and amorphous regions. Groups other than amide, respectively, may be present in minor amounts in these polymers, such groups including: carbonate, urea, urethane, ether, ketone, imidazole, oxazole, and other oxygen-containing moieties.

In general, these high molecular weight polyamides are obtained by reacting polyamines, such as the alpha,

omega-diamines, like l,6-hexamethylene diamine, 1,5- pentamethylene diamine and 1,8-octamethylene diamine, with polycarboxylic acids, such as adipic acid, succinic acid, phthalic acid, chlorophthalic acid and the like. The polyamides may also be prepared by polymerization of aminocarboxylic acids, such as aminocaproic acid. Polyamides from caprolactam and p-aminobenzoic acid also can be used.

The high molecular weight aromatic polyamides are obtained by condensation of metaphenylene diamines with isophthalic acid or paraphenylene diamines with terephthalic acids or m, p, or o-benzamides or mixtures of the above isomeric amines with isomeric acids. It is also possible to make polyamides using the above mentioned isomers with substituents on the phenyl groups, halogen (Cl), alkyl (CH etc., or to use biphenyl acids with diamines or aromatic diamines and/or diacthe adhesive on the element, the adhesive containing ids in which the aromatic nuclei are spaced by:

Tit 0 N-N ,-CH -;-C-,- ll N I l l O -C CH 0 Instead of phenylene groups, the polymers can partly or totally contain heterocyclic rings.

Examples of such materials are polyhexamethylene adipamide, copolymers of metaphenylene diamine and terephthalic or isophthalic acid or acid chloride, poly[- bis-(4-amino-cyclohexyl)methanedodecamide], polypara-phenylene terephthalamide from phenylenediamine and terephthaloyl chloride, po1y(hexamethylene terephthalamide), poly-m, or p-benzamide and the like. Examples of commercially available aliphatic polyamides are nylon 6 and nylon 66. Examples of aromatic polyamides are Nomex and Fiber B (the aromids or aramids").

Preferred are the linear or long chain synthetic aromatic polyamides in which at least 85% of the amide linkages are attached directly to aromatic rings, which are highly crystalline, and which have a modulus (grams/denier) of at least about 350.

Polyamides and methods for making them are well known as shown by U.S. Pat. Nos. 2,071,250; 2,071,253; 2,130,948; 2,241,321; 3,006,899; 3,094,511; 3,225,011; 3,232,910; 3,308,007; 3,464,878; 3,536,651; 3,629,053; 3,632,548;

3,660,361; and 3,673,143; Belgian Pat. No. 726,050; French Pat. No. 1,526,745; British Pat. No. 1,259,788; Mechanics of Pneumatic Tires, Clark, National Bureau of Standards Monograph 122, U.S. Department of Commerce, issued Nov., 1971, pages 225 to 238; and Rubber World, April, 1972, page 56. More information on polyamides, especially those for use in making fibers, can be found in Encyclopedia of Polymer Science and Technology, Interscience Publishers division of John Wiley and Sons, Inc., New York, 1969, Volume 10, pages 347 to 460 and, more particularity with respect to high modulus fibers, in Chem Tech, Preston, November, 1971, pages 664 to 671; American Chem. Soc. Polym. Prepr., Bach et a1, 11(1), 334 (1970); Journal of Polymer Science, Frazer et a1, Part A, Volume 2, pages 1147 to 1169 (1964); and the Federal Register,v Volume 37, No. 120, June 21, 1972, pages 12243 and 12244.

The type of rubber latex used in the tire cord dip bath of this invention is a latex of a copolymer of a vinyl pyridine and conjugated diolefin having 4 to 6 carbon atoms. The rubber latex is of the type described in U.S. Pat. No. 2,561,215 and comprises an aqueous dispersion of a copolymer of 50 to 95 by weight of a conjugated diolefin having 4 to 6 carbon atoms, 5 to 40 of a vinyl pyridine and to 40 of a styrene. Examples of suitable vinyl pyridines are 2-viny1 pyridine, 4-vinyl pyridine, 2-methyl-5-vinyl pyridine, and 5-ethy1-2-vinyl pyridine.

In practicing this invention, it is usually preferred to use a latex of a copolymer of from about 60 to 80% by weight butadiene-1,3, 7 32% styrene and 5 to 22% of 2-vinyl pyridine. Excellent results are obtained using a latex of a terpolymer of about 70% by weight of butadiene-l,3, styrene and 15% 2-vinyl pyridine having a total solids contents of around 30 to 50% by weight.

and

Also, blends of latices may be used such as a blend of a butadiene-l ,3/2-viny1 pyridine rubbery copolymer latex and a butadiene-l,3/styrene rubbery copolymer latex or a blend of a butadiene-1/3styrene/2-vinyl pyridine rubbery copolymer latex and a butadiene- 1,3/styrene rubbery copolymer latex so long as the percent by weight ratio of total monomers in the copolymers is within the ranges as specified above. The pH of the latices should be similar and the surfactants and stabilizers should be compatible to avoid coagulation on blending or mixing of the latices. Further disclosures of rubbery vinyl pyridine copolymer latices may be found in U.S. Pat. Nos. 2,615,826 and 3,437,122.

The trimethylol phenol is prepared by the reaction of an excess of formaldehyde with phenol using a catalytic amount of base (NaOI-l) under nitrogen. The excess of H CO drives the reaction to a high content of trimethylol phenol (2,4,6-trimethylol phenol) which is water soluble. The unreacted aldehyde can be removed by venting with reduced pressure. The base can be neutralized with acid to a pH of about 7. In preparing trimethylol phenol, after the first mol of formaldehyde has added to the phenol, the second and third additions are easier.

The resorcinol compound is resorcinol or a water soluble, thermoplastic and non-heat hardenable (without a curing agent or crosslinker) resorcinol-formaldehyde novolak or novolak resin or mixture thereof. The novolaks are prepared under acid conditions by the reaction of resorcinol and formaldehyde (or a formaldehyde donor like paraformaldehyde) to provide compounds having reactive phenolic hydroxy groups rather than methylol groups. The mol ratio of resorcinol to formaldehyde can vary over a considerable range to provide novolaks useful in the practice of the present invention although a preferred mol ratio of resorcinol to formaldehyde is about 1:05 to 2.0. These compounds and methods for making them are well known in the art.

Examples of commercially available resorcinol compounds are the water soluble novolak resins known as Arofene 779 (Ashland Chemical Co.) having a mol ratio of resorcinol to formaldehyde of about 1/0.62 and a commercially available novolak which comprises a mixture of about 15 parts by weight of resorcinol, 42.5 parts of diresorcinol methane (R/F/R) and 42.5 parts of low molecular weight R/F novolak resin of a R/F mol ratio of about 3/2.

Since the resorcinol compound is acidic or prepared under acidic conditions, it should be neutralized or sufficient base such as NH OH or NaOI-I added to it to prevent coagulation of the latex when the resorcinol compound is mixed with the latex. Even though the latex is alkaline, sufficient additional base may still be necessary to prevent such coagulation or premature coagulation and the consequent inability to use the dip properly.

Information on the preparation of the novolaks will be found in Encyclopedia of Chemical Technology,

cinol compound, to reduce viscosities, and for the I proper solids content to get the necessary pick-up of solids on and penetration between the fibers of the cord.

Based on 100 parts by weight (dry weight) of the vinyl pyridine rubber copolymer, or blend of the same, the dip generally comprise the rubber, from about 2 to 28 parts by weight of the trimethylol phenol, from 20 about 0.5 to 24 parts by weight of the resorcinol compound, from about to 3.0 parts by weight of water soluble base such as NI-l or NaOI-I to provide a pH of at least 7.0, and from about 7.0, and from about 170 to 1100 parts by weight of water.

In order to provide data for the tire cord adhesive of this invention, a standard single-cord I-l-pull test is employed to determine the static adhesion at room temperature and above of the adhesivecoated tire cord to rubber. All the data submitted herein including the ex- 3 In order to apply the latex adhesive to the cords in a reliable manner, the cords are fed through the adhesive dip bath while being maintained under a small predetermined tension and into a drying oven where they are stretched and dried under a predetermined tension (about 2% to prevent sagging). As the cords leave the oven they enter a cooling zone where they are air cooled before the tension is released. In each case the adhesive-coated cords leaving the dip are dried in the oven at from about 200 to 500F. for from about 5-300 seconds while under some tension. The drying and/or curing of the adhesive treated cord may be accomplished in one or more ovens for different times, temperatures and tensions. The time the cord remains in the one-step adhesive dip is about a second or so or at least for a period of time sufficient to allow wetting of the cord and penetration of the fibers of the cord.

The single-cord I-I-pull test is then employed to determine the static adhesion of the dried adhesive coated synthetic fiber cords to rubber. In each case the rubber 55 test specimens are made from the same standard type rubber composition using the following recipe:

-Continued Parts by Material Weight 5 Processing oil (a blend of highly aromatic petroleum fractions) 5.0 Zinc oxide 3.0 Stearic acid 1.5 Cohedur RL (a 1 :1 mixture of resorcinol and Cohedur A (the pentamethyl ether of hexamethylol melamine) which is a colorless, viscous liquid which liberates l0 formaldehyde on heating. Naftone, Inc.) 4.7

- N-ten-butyl-2-benzothiazole-sulfenamide (Santocure NS, Monsanto Chemical Co.) 1.2 Sulfur 3.0

In every case the cords to be tested are placed in parallel positions in a multiple-strand mold of the type described in the singlecord H-pull adhesion test ASTM designated D 2138-67, the mold is filled with unvulcanized rubber of the above composition, the cords being maintained under a tension of 50 grams each, and the rubber is cured minutes at around 315F. to the elastic state. Each rubber test specimen is 0 inch thick and has a inch cord embedment.

After the rubber has been cured, the hot reticulate cured rubber piece is removed from the mold, cooled 5 and H-test specimens are cut from said piece, each specimen consisting of a single cord encased in rubber and having each end embedded in the center of a rubber tab or embedment having a length of around 1 inch or so. The specimens are then aged at least 16 hours at 0 room temperature. The force required to separate the cord from the rubber is then determined at room temperature or 250F. using an INSTRON tester provided with specimen grips. The maximum force in pounds required to separate the cord from the rubber is the H- adhesion value.

Cords or fabric coated with the adhesive of the present invention using the one-step or single dip of thisinvention can have from about 0.5 to 7% by weight (dry) solids of the adhesive dip on the cord based on the weight of the cord and can be used in the manufacture of carcasses, belts, flippers and chafers of radial, bias, or belted-bias passenger tires, truck tires, motorcycle and bicycle tires, off-the-road tires and airplane tires, and, also, in making transmission belts, V-belts, conveyor belts, hose, gaskets, rubbers, tarpaulins and the less otherwise indicated.

EXAMPLE I CORD DIP COMPOSITIONS Material A B Vinyl pyridine rubber latex (1) g. 100g. Trimethylol phenol (2) 5g. 10g. Resorcinol-formaldehyde resin (3) 5g. 10g. Concentrated ammonium hydroxide l0 I0 (28% NH in H O) drops drops Water 50g. 50g.

Part of the water was used to dilute the viscous trimethylol phenol and another part after the addition of the ammonium hydroxide was used to dilute the resorcinol-formaldehyde resin. Thereafter the diluted solutions were mixed with the vinyl pyridine latex.

Polyamide tire cords (4) were then dipped in the foregoing dips and were heat treated under stretch (about 2%) at 450F. for 90 seconds in air, laminated with the standard type rubber stock described supra, and molded, and the resulting assembly was cured for 30 minutes at 315F. After curing, the assembly was removed from the mold, cooled and tested according to the I-Iadhesion test described supra. The following H- adhesions were obtained for the cords treated as described above. Dip A: 63 lbs. and Dip B: 67 lbs. Notes: 7

l. Aqueous alkaline (about pH 10.5 10.7) dispersion ofa terpolymer of 70 parts by weight of butadiene- 1,3, 15 parts of styrene and I5 parts of 2-vinyl pyridine. 41% by weight total solids (about 38% by weight rubber solids, balance surfactant, stabilizer, etc.).

2. 60% total solids in H O, Union Carbide Bakelite BRL-l03 l.

3. 50% total solids in H O, preformed water-soluble resorcinol-formaldehyde novolak resin, Koopers Co., Inc., Penacolite R-2170.

4. du Pont Fiber B (1500/3). a long chain synthetic aromatic polyamide (poIy-p-phenylene terephthalamide) in which at least 85% of the amide linkages are attached directly to aromatic rings, which is highly crystalline, and which has a denier of 4500, a breaking strength of 180 lbs., a tenacity of 18 grams/denier, an elongation at break of 4%, a modulus of 350 grams/- denier, a loop tenacity of 8.0 grams/denier, a growth and creep of 0.49% (lgpd, 30 minutes, 75F), and a 160C. shrinkage of Instead of preparing the tire cord adhesive as described earlier in this example, the dip can be prepared as follows: add the concentrated ammonia to the water, then dissolve. the. resorcinol-formaldehyde resin (dry form) in the water-NI-I mix, next add the vinyl pyridine latex 14% solids), and finally add the trimethylol phenol (as 30% solids in H O).

EXAMPLE II TABLE I H-Adhesions in Different Compounds and Different Temperatures Stock H at RT* H at 250F.

Same as Example I 70 lbs. 54 lbs. Same as Example I without Cohedur RL 66 lbs. 50 lbs.

Room temperature, about 25C.

EXAMPLE III The method of this example was the same as that of Example I, above, except that Dip B was diluted with more water to lower the total solids (T.S.) content of the dip. After curing in the same type rubber stock, I-I adhesion tests were run and the results of the tests are shown below in Table II.

TABLE I1 Influence of TS on the H-Adhesion 5 TS in (by weight of aqueous dispersion) RT adhesion 250F. adhesion I7 /z 68 lbs. 52 lbs. I5 68 lbs. 58 lbs. I3 70 lbs. 60 lbs.

EXAMPLE IV The method of this example was the same as that of Example I, B above, except for variations in concentra-. tions of the water as shown below:

Composition of Dip Vinyl pyridine latex (41% total solids) 100g.

Trimethylol phenol (60% total solids in H O) 10g. Resorcinol-formaldehyde novolak resin (50% total solids in H O) IOg.

2O Concentrated Ammonia (28-30% in H 0) 10 drops Water variable At intervals of time (aging), the polyamide cord was dipped in dips of different total solids by dilution with water, heat treated at 450F. for 90 seconds and cured into the same type of standard stocks. The following H- adhesions were obtained after testing:

H-adhesion in lbs. Hot adhesions indicated by RT-room temperature, about 25C.

The results of these tests show that the dips of the present invention have a shelf-life of at least 4 weeks.

EXAMPLE V The method of this Examples was the same as that of Example IV, above, and also of Example I, B, above, except that the resorcinolformaldehyde resin used was replaced with other resorcinol compounds in varying amounts. The concentration (dry solids or weight) of the resorcinol compound is used in Table IV, below, rather than the weight of the resin solution. The compounds used and the l-I-adhesion test results are shown below:

TABLE IV Resorcinol Compound Parts I-I-Adhesion, lbs, RT

Arofene 7209 6 g. 67 EO32702-22.2 7.5 g. 66 Arofene 779' 2.5 g. 70 Arofene 6714' 2.5 g. 67 Resorcinol 2.5 g. 62 Resorcinol-formaldehyde compound (Novolak) (R/F=2/1)* 5 64 TABLE IV Continued Resorcinol Compound Parts H-Adhesion, lbs. RT

Resorcinol-formaldehyde compound (Novolak) IF 1/ l Resorcinol-formaldehyde compound (Novolak) (R/F 2/3)* Resorcinol-formaldehyde compound (Novolak) F 3/ 5)* EXAMPLE VI A concentrated tire cord dip was first prepared by adding to 100 parts of a 41% (by weight total solids) vinyl pyridine latex first parts of a 30% trimethylol phenol solution (BRL 1031) and then 5 parts ofa 50% total solids aqueous resorcinol-formaldehyde novolak solution (Penacolite R 2170) which was first made alkaline with a few drops of concentrated ammonia. The viscosity of the resulting aqueous dip (40% TS), which was initially 12 centipoises (cp), increased to cp after 20 days and to 24.5 cp after 31 days.

The adhesive properties of the dip were tested by taking a sample of the dip, diluting it with 200 parts of water to 15% by weight total solids and using it as a cord dip for Fiber B. The freshly prepared dip showed an H-adhesion of 7] lbs. at RT. After 10 days, the H- adhesion was 69 lbs. at RT, and after 34 days, it was 68 lbs. at RT.

In this example, except where noted, the chemical compounds, the cord used, and the processing and testing procedures were the same as in Example I, above.

EXAMPLE VII The method of this Example was the same as that of Example I, above, except that in the dips containing the vinyl pyridine latex either the resorcinol-formaldehyde resin or the trimethylol phenol was omitted from the dip composition. The H-adhesions obtained are shown below:

Dry weight of TM? or R-F resin and based on 100 g. of the (41% T.S.) vinyl pyridine rubber latex.

These results show that omission of either the resorcinolformaldehyde resin (or the resorcinol compound) or of the trimethylol phenol from the dip containing the vinyl pyridine latex results in a substantial loss of H-adhesion.

Also, in this example the pulled-out cords from the I-I-adhesion tests were light colored which means that the failure occured mainly between the cord and the rubber stock (standard type). On the other hand with the dips of the present invention the pulled-out cords from the H-adhesion test are black, rubber covered indicating that failure occurred in the rubber phase (standard type stock).

EXAMPLE VIII It is possible to use a styrene-butadiene latex (for instance SBR 2000) to substitute for part of the vinyl pyridine latex as is shown in the following dip compositions:

- Parts Parts Dip Compositions Dip A Dip B Vinyl pyridine latex (TS 41% by weight) 80 50 SBR 2000 (copolymer of about 54% BDN and 46% STY, hot emulsion polymerized latex, 42% by weight T.S., about 39.5% rubber solids. balance surfactant, stabilizer, etc., pH about lO.5-l 1.5) 20 50 Trimethylol phenol 30% T5. in water (BRL l03l) l5 l5 Resorcinol novolak 50% T5. in water (Penacolite R 2170) (made alkaline with ammonia) 5 5 Water l 10 l 10 H-adhesion in lbs. (RT) 65 64 The cord and chemicals used (except for the SBR 2000) and the processing and testing procedures employed were the same as in Example I, above.

EXAMPLE IX H-Adhesion, 25C.

Nylon 66, 840 denier 63 lbs.

(840/2/2, du Pont) Dacron (1300/3. polyethylene 1 1 lbs.

terephthalate. du Pont) These results show that the clips of the present invention can be used for other polyamide fabrics but are not satisfactory for polyester tire cord fabric.

EXAMPLE X An aqueous alkaline dip, about 40% total solids, of by weight of the vinyl pyridine latex and 25% by weight of the SBR 2000 latex was mixed with various amounts of BRL 1031 and Penacolite R 2170. See Example I, above. The viscosities of the dips were obseconds and embedded in the standard rubber stock as shown in Example 1, supra, and cured. On testing the cured rubber embedded cords, the cords exhibited H- adhesions at room temperature of 63 to 66 pounds. Dry aging of the cured rubber embedded cords (300F. for

dips were aged prior to dipping the Fiber B (1500/3) cords; and the processing, drying, rubber embedment.. curing and testing of the cords is the same as for said Examples.

TABLE VII H-Adhesions After Aging Dips Resin Component H-Adhesion. lbs. RT

24 hours under nitrogen in a sealed container) reduced Penacolite R 2170. 0.625 hr 63 the I-l-adhesions at room temperature about 3 pounds. penacohfe R 2170- 70 w fth d b b dd d d (3000: Penacollte R 2170. 1.56 phr 68 et aging o e cure ru er em e e cor s ResorcmoL L25 65 for 24 hours 1n water under nitrogen in a sealed con- Resorcinol, 1.56 phr" 64 tainer) reduced the H-adhesions at room temperature I [5 Dip aged 5 hours at 50C.. vlscosny 14 to 15 cp. to pounds "Dip aged 4 hours at 50C.. no measurable viscosity change TABLE V Change of Viscosity with Time Parts by wt. Parts by wt.

(dry) of BRL (dry) of 1031 per 100 Penacolite parts by wt. R 2170 per (dry) of 100 parts by rubber wt. (dry) of Viscosity, cp after:

blend rubber blend 1 day 10 days 21 days days A 6.5 6.0 10.0 10.0 10.5 11.5 B 7.5 5.0 10.0 11.5 11.5 11.5 C 8.4 4.0 11.0 12.0 12.0 12.0 D 9.45 3.0 11.5 12.0 12.0 12.0

cp: centipoise 3O EXAMPLE XI EXAMPLE XIII TABLE VI Delayed Addition of Penacolite R 2170 On Adhesions Parts by wt.

Parts by wt. (dry) of (dry) of BRL Penacolite 1031 per. 100 R2170 per parts by wt. 100 parts by (dry) of wt. (dry) of I-I-Adhesions, lbs.

rubber blend rubber blend RT 250F.

EXAMPLE XII The methods of this example were similar to those of Examples X and XI, above: the aqueous alkaline dip contained 15% total solids; the same latex blend was used; and 15 parts by wt. (dry) of BRL 1031 were used per 100 parts by wt. (dry) of the rubber blend. Different levels of alkaline Penacolite R 2170 (dry weight per 100 parts dry rubber) and resorcinol were used. The

An aqueous alkaline dispersion or emulsion dip was prepared as shown by Example 1, above, containing parts by weight (dry) of the vinyl pyridine rubber, 9.8 parts by weight of the resorcinol-formaldehyde novolak resin (Penacolite R 2170), 0.7 part of NI-I OH, 17.6 parts of trimethylol phenol (BRL 1031) and 673 parts of water. Fiber B cords (1500/3) were passed through the dip and dried in a first oven under 7 pounds tension at 350F. for seconds. The cords were next passed through a second oven under 15 pounds tension at 475F. for 90 seconds. Part of the cords were then embedded in the rubber stock and cured. The results on testing as in Example 1, above, were as follows:

H-adhesion at RT was 57.6 lbs.

Modulus was 439 grams/denier.

Test on dried adhesive containing cord no rubber embedment. Test was ASTM Part 24, D885-21, as modified.(the initial modulus of the dipped and dried cord is calculated in the 3 to 4 g/d portion of the load vs. elongation curve rather than at 10% elongation because Fiber B breaks at about 5% elongation).

Breaking strength was 192 lbs. Test was ASTM Part 24, D885-15 on dried adhesive containing cord no rubber embedment.

Repeating the method of this example with average temperatures of 300-350F. in the first oven at Fiber B (1500/3) cord tensions of 1, 4 and 7 pounds, the moduli obtained were 389, 425, and 413 g/d (Av. 409) and the breaking strengths obtained were 202, 202 and 193 pounds (Av. 199), respectively. Similarly, with average Fiber B (1500/3) cord tensions of 1-7 pounds on the cord in the first oven at first oven temperatures of 300 and 350F., the moduli obtained were 389 and 428 g/d (Av. 409) and the breaking strengths obtained were 198 and 201 pounds (Av. 199), respectively. The average room temperature H-adhesion for these runs was 54 pounds.

derivative of glycerol having an epoxide equivalent of 150-170 and a viscosity of 120-200 centipoises) and NaOH. The second dip comprised an aqueous alkaline dispersion (about 22% solids) of about 100 pbw of the above vinyl pyridine rubber, 0.3 phr of a defoamer, 3.2 phr of NH OH and 17.3 phr of a NaOH catalyzed resorcinolformaldehyde (1 H6 pbw ratio) resin. The Fiber B (1500/3) cords were dipped in the first dip and then at a tension of l-7 pounds dried at 300-350F. for 120 seconds in a first oven after which they were dried further at 475F. for 45 seconds under a tension of pounds. Next, the dried and dipped cords were dipped in the second dip and dried at 475 F. for seconds at a tension of 15 pounds. On testing the following results were obtained:

H-adhesions, room temperature: 63-65 pounds, average 64 pounds.

Moduli: 328-356, average 338 g/d.

Breaking strength: l88-l95, average 191 pounds.

The increased moduli of the dipped cords of the pres- 2 ent invention may lead to better tread wear when they are used in the belts of radial or bias-belted tires.

While in the foregoing examples, the adhesive containing polyamide reinforcing elements can be adhered to a vulcanizable blend of natural rubber, polybutadiene rubber, and rubbery butadienestyrene copolymer by curing the same in combination together, it is apparent that said heat cured adhesive containing polyamide reinforcing element can be adhered to other vulcanizable rubbery materials, by curing or vulcanizing the same in combination with the rubber, such as one or more of the foregoing rubbers as well as nitrile rubbers, chloroprene rubbers, polyisoprenes, vinyl pyridine rubbers, acrylic rubbers, isoprene-acrylonitrile rubbers and the like and mixtures of the same. These rubbers can be mixed with the usual compounding ingredients including sulfur, stearic acid, zinc oxide, magnesium oxide, accelerators, antioxidants and other curatives, rubber compounding ingredients and the like well known to those skilled in the art for the particular rubbers being employed.

What is claimed is:

l. A method for adhering a polyamide reinforcing element to a rubber compound which comprises treating said element with a composition consisting essentially of an aqueous alkaline dispersion of 100 parts by weight of a rubbery vinyl pyridine copolymer, from about 2 to 28 parts by weight of trimethylol phenol, from about 0.5 to 24 parts by weight of a least one water soluble, thermoplastic and non heat hardenable resorcinol compound selected from the group consisting of resorcinol and a resorcinol-formaldehyde novolak, from about 0 to 3 parts by weight of an alkaline material selected from the group consisting of NH and NaOH, and from about 170 to l 100 parts by weight of water, heating said treated element at a temperature and for a period of time sufficient to remove essentially all of the water from said composition and to leave on said element a heat cured adhesive in an amount of 6 from about 0.5 to 7% by weight (dry) based on the weight of said reinforcing element, combining said dried and heat cured adhesive containing reinforcing element with an unvulcanized rubber compound, and vulcanizing the same.

2. A- method for adhering a polyamide reinforcing element-to'arubber compound which comprises treating said element with a composition consisting essentially of an aqueous alkaline dispersion of 100 parts by weight of a rubbery vinyl pyridine copolymer, from about 2 to 28 parts by weight of trimethylol phenol, from about 0.5 to 24 parts by weight of at least one water soluble, thermoplastic and non heat hardenable resorcinol compound selected from the group consisting of resorcinol and a resorcinol-formaldehyde novolak, from about 0 to 3 parts by weight of an alkaline material selected from the group consisting of NH and NaOH, and from about 170 to l 100 parts by weight of water, heating said treated element under tension at a temperature of from about 200 to 500F. for from about 5 to 300 seconds to remove essentially all of the 0 water from said composition and to leave on said element a heat cured adhesive in-an amount of from about 0.5 to 7 by weight (dry) based on the weight of said reinforcing element, combining said dried and heat cured adhesive containing reinforcing element with an unvulcanized rubber compound, and vulcanizing the same.

3. A method according to claim 2 where said rubbery vinyl pyridine copolymer is a copolymer of from about 60 to by weight of butadiene-l ,3, from about 7 to 0 32% by weight of styrene, and from about 5 to 22% by weight of 2-vinyl pyridine and where said resorcinol compound is made by reacting resorcinol with formaldehyde in the mol ratio of about 1:05 to 2.

4. A method according to claim 3 where said copolymer is a blend of a terpolymer of butadiene-l ,3, styrene and 2-vinyl pyridine and a copolymer of butadiene-l ,3 and styrene.

5. A method according to claim 3 where said reinforcing element is a cord of a linear long chain synthetic aromatic poly-p-phenylene terephthalamide in which at least of the amide linkages are attached directly to aromatic rings, which is highly crystalline, and which has a modulus (grams/denier) of at least about 350.

6. The product produced by the method of claim 1.

7. The product according to claim 6 in which the polyamide reinforcing element is a cord of a linear long chain synthetic aromatic poly-p-phenylene terephthalamide in which at least 85% of the amide linkages are attached directly to aromatic rings, which is highly crystalline, and which has a modulus (grams/denier) of at least about 350.

8. A bonded composite material comprising a polyamide reinforcing element embedded in a vulcanized rubber, said element containing from about 0.5 to 7% by weight (dry) based on the weight of said element of a heat cured adhesive composition consisting essentially of parts by weight of a rubbery vinyl pyridine copolymer, from about 2 to 28 parts by weight of trimethylol phenol and from about 0.5 to 24 parts by weight of at least one water soluble thermoplastic and non heat hardenable resorcinol compound selected from the group consisting of resorcinol and a resorcmol-formaldehyde novolak and said composition forming a bond between said element and said rubber. 9. A bonded composite material according to claim 8 where said rubbery vinyl pyridine copolymer is a copolymer of from about 60 to 80% by weight of butadipolymer of butadiene-l ,3 and styrene.

11. A bonded composite material according to claim 9 where said element is a cord of a linear long chain synthetic aromatic poly-p-phenylene terephthalamide in which at least of the amide linkages are attached directly to aromatic rings, which is highly cyrstalline, and which has a modulus (grams/denier) of at least about 350. 

1. A METHOD FOR ADHERING A POLYAMIDE REINFORCING ELEMENT TO A RUBBER COMPOUND WHICH COMPRISES TREATING SAID ELEMENT WITH A COMPOSITION CONSISTING ESSENTIALLY OF AN AQUEOUS ALKALINE DISPERSION OF 100 PARTS BY WEIGHT OF A RUBBERY VINYL PYRIDINE COPOLYMER, FROM ABOUT 2 TO 28 PARTS BY WEIGHT OF TRIMETHYLOL PHENOL, FROM ABOUT 0.5 TO 24 PARTS BY WEIGHT OF A LEAST ONE WATER SOLUBLE, THERMOPLASTIC AND NON HEAT HARDENABLE RESORCINOL COMPOUND SELECTED FROM THE GROUP CONSISTING OF RESORCINOL AND A RESORCINOL-FORMALDEHYDE NOVOLAK, FROM ABOUT 0 TO 3 PARTS BY WEIGHT OF AN ALKALINE MATERIAL SELECTED FROM THE GROUP CONSISTING OF NH3 AND NAOH, AND FROM ABOUT 170 TO 1100 PARTS BY WEIGHT OF WATER, HEATING SAID TREATED ELEMENT AT A TEMPERATURE AND FOR A PERIOD OF TIME SUFFICIENT TO REMOVE ESSENTIALLY ALL OF THE WATER FROM SAID COMPOSITION AND TO LEAVE ON SAID ELEMENT A HEAT CURED ADHESIVE IN AN AMOUNT OF FROM ABOUT 0.5 TO 7% BY WEIGHT (DRY) BASED ON THE WEIGHT OF SAID REINFORCING ELEMENT, COMBINING SAID DRIED AND HEAT CURED ADHESIVE CONTAINING REINFORCING ELEMENT WITH AN UNVULCANIZED RUBBER COMPOUND, AND VULCANIZING THE SAME.
 2. A method for adhering a polyamide reinforcing element to a rubber compound which comprises treating said element with a composition consisting essentially of an aqueous alkaline dispersion of 100 parts by weight of a rubbery vinyl pyridine copolymer, from about 2 to 28 parts by weight of trimethylol phenol, from about 0.5 to 24 parts by weight of at least one water soluble, thermoplastic and non heat hardenable resorcinol compound selected from the group consisting of resorcinol and a resorcinol-formaldehyde novolak, from about 0 to 3 parts by weight of an alkaline material selected from the group consisting of NH3 and NaOH, and from about 170 to 1100 parts by weight of water, heating said treated element under tension at a temperature of from about 200* to 500*F. for from about 5 to 300 seconds to remove essentially all of the water from said composition and to leave on said element a heat cured adhesive in an amount of from about 0.5 to 7% by weight (dry) based on the weight of said reinforcing element, combining said dried and heat cured adhesive containing reinforcing element with an unvulcanized rubber compound, and vulcanizing the same.
 3. A method according to claim 2 where said rubbery vinyl pyridine copolymer is a copolymer of from about 60 to 80% by weight of butadiene-1,3, from about 7 to 32% by weight of styrene, and from about 5 to 22% by weight of 2-vinyl pyridine and where said resorcinol compound is made by reacting resorcinol with formaldehyde in the Mol ratio of about 1:0.5 to
 2. 4. A method according to claim 3 where said copolymer is a blend of a terpolymer of butadiene-1,3, styrene and 2-vinyl pyridine and a copolymer of butadiene-1,3 and styrene.
 5. A method according to claim 3 where said reinforcing element is a cord of a linear long chain synthetic aromatic poly-p-phenylene terephthalamide in which at least 85% of the amide linkages are attached directly to aromatic rings, which is highly crystalline, and which has a modulus (grams/denier) of at least about
 350. 6. The product produced by the method of claim
 1. 7. The product according to claim 6 in which the polyamide reinforcing element is a cord of a linear long chain synthetic aromatic poly-p-phenylene terephthalamide in which at least 85% of the amide linkages are attached directly to aromatic rings, which is highly crystalline, and which has a modulus (grams/denier) of at least about
 350. 8. A bonded composite material comprising a polyamide reinforcing element embedded in a vulcanized rubber, said element containing from about 0.5 to 7% by weight (dry) based on the weight of said element of a heat cured adhesive composition consisting essentially of 100 parts by weight of a rubbery vinyl pyridine copolymer, from about 2 to 28 parts by weight of trimethylol phenol and from about 0.5 to 24 parts by weight of at least one water soluble thermoplastic and non heat hardenable resorcinol compound selected from the group consisting of resorcinol and a resorcinol-formaldehyde novolak and said composition forming a bond between said element and said rubber.
 9. A bonded composite material according to claim 8 where said rubbery vinyl pyridine copolymer is a copolymer of from about 60 to 80% by weight of butadiene-1,3, from about 7 to 32% by weight of styrene, and from about 5 to 22% by weight of 2-vinyl pyridine and where said resorcinol compound is made by reacting resorcinol with formaldehyde in the mol ratio of about 1:0.5 to
 2. 10. A bonded composite material according to claim 9 where said copolymer is a blend of a terpolymer of butadiene-1,3, styrene and 2-vinyl pyridine and a copolymer of butadiene-1,3 and styrene.
 11. A bonded composite material according to claim 9 where said element is a cord of a linear long chain synthetic aromatic poly-p-phenylene terephthalamide in which at least 85% of the amide linkages are attached directly to aromatic rings, which is highly cyrstalline, and which has a modulus (grams/denier) of at least about
 350. 